三甲基膦支持的硒配位铁、钴配合物的合成和性质
发布时间：2018-12-09 15:40
【摘要】：过渡金属氢化物是一类重要的金属有机化合物,在催化化学、合成化学和化学工业等各个领域有广泛的应用。人们已经合成出了一系列的过渡金属氢配合物,并且发现很多的金属氢化物在烯烃、炔烃、CO2、羰基化合物的活化还原以及醇的脱氢反应中有很好的催化效果。其中又以含有钌、铑、铱等贵金属的氢化物居多,相对比而言廉价金属来源更加广泛,对环境也更加友好;因此探索可以替代的廉价金属的氢化物成为新的研究热点。到目前为止,已有很多关于廉价金属氢化物的制备以及催化应用的报道,尤其是铁氢配合物;已有文献报道部分铁氢配合物在催化应用中具有与贵金属氢化物相似的催化活性;关于钴氢配合物直接参与催化反应的报道虽少,但根据已报道的文献可知,钴氢配合物是多种催化反应的活性中间体,具有极大的发展潜力。本论文主要从以下两部分展开,第一部分我们研究了 Co(PMe3)4与苯硒酚、邻甲基苯硒酚、对甲氧基苯硒酚的反应,成功得到了四种新型的含硒配位的有机钴配合物1-4。对Co(PMe3)4与苯硒酚系列配体反应的机理进行了探究,同时新型的钴氢配合物7通过PhSeLi,CoCl(PMe3)3以及PhSH三组分反应得到。通过对新合成的含硒配位的有机钴配合物的性质进行探索,发现钴氢配合物2对醛酮的硅氢化反应有一定的催化效果,配合物3、4可以与CO进一步反应得到双羰基钴配合物5和6。第二部分在实验室已有的实验成果基础上对(o-PPh2)PhSeH与Fe(PMe3)4反应得到的铁氢配合物进行系统的性质探索,从铁氢配合物与CO的反应中,我们分离出了含有两种异构体的羰基铁氢配合物8;铁氢配合物与乙酰丙酮的反应,经过单晶衍射验证生成了双螯合铁配合物11。此外,我们研究了(o-PPh2)PhSeH 与 Co(PMe3)4、CoCl(PMe3)3、CoMe(PMe3)4 的反应,均得到双螯合钴配合物14。
[Abstract]:Transition metal hydride is an important class of organometallic compounds, which has been widely used in catalytic chemistry, synthetic chemistry and chemical industry. A series of transition metal hydrogen complexes have been synthesized and many metal hydride have been found to have good catalytic effects in the activation and reduction of alkenes alkynes and CO2, carbonyl compounds as well as the dehydrogenation of alcohols. Among them, the hydride containing ruthenium, rhodium, iridium and other precious metals is more common, compared with cheap metal sources more extensive, more environmentally friendly; therefore, the exploration of cheap metals can be replaced by hydride has become a new research hotspot. Up to now, there have been a lot of reports on the preparation and catalytic application of cheap metal hydride, especially the iron hydrogen complexes, and some of the iron hydrogen complexes have similar catalytic activity to the noble metal hydride in the catalytic application. Although there are few reports on the direct participation of cobalt hydrogen complexes in catalytic reactions, according to the reported literature, the cobalt hydrogen complexes are active intermediates of various catalytic reactions and have great potential for development. In the first part, we studied the reaction of Co (PMe3) 4 with phenylselenol, o-methylphenylselenol and p-methoxyphenylselenol, and successfully obtained four new organic cobalt complexes 1-4 containing selenium. The mechanism of the reaction of Co (PMe3) 4 with phenylselenol ligands was investigated. A new cobalt hydrogen complex 7 was obtained by the reaction of PhSeLi,CoCl (PMe3) 3 and PhSH. By exploring the properties of the newly synthesized organic cobalt complexes containing selenium, it is found that cobalt hydrogen complex 2 has a certain catalytic effect on the hydrosilylation of aldehydes and ketones. Complex 3H4 can be further reacted with CO to obtain cobalt bicarbonyl complexes 5 and 6. In the second part, based on the experimental results in the laboratory, the properties of the ferric hydrogen complexes obtained by the reaction of (o-PPh2) PhSeH with Fe (PMe3) 4 were investigated systematically, and the reaction of the ferric hydrogen complexes with CO was carried out. The carbonyl iron hydrogen complex 8 containing two isomers was isolated. The reaction of ferric hydrogen complex with acetylacetone was studied and the double chelate iron complex 11 was obtained by single crystal diffraction. In addition, the reaction of (o-PPh2) PhSeH with Co (PMe3) _ 4 Cocl (PMe3) _ 3 (PMe3) _ 4 has been studied.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2369634
[Abstract]:Transition metal hydride is an important class of organometallic compounds, which has been widely used in catalytic chemistry, synthetic chemistry and chemical industry. A series of transition metal hydrogen complexes have been synthesized and many metal hydride have been found to have good catalytic effects in the activation and reduction of alkenes alkynes and CO2, carbonyl compounds as well as the dehydrogenation of alcohols. Among them, the hydride containing ruthenium, rhodium, iridium and other precious metals is more common, compared with cheap metal sources more extensive, more environmentally friendly; therefore, the exploration of cheap metals can be replaced by hydride has become a new research hotspot. Up to now, there have been a lot of reports on the preparation and catalytic application of cheap metal hydride, especially the iron hydrogen complexes, and some of the iron hydrogen complexes have similar catalytic activity to the noble metal hydride in the catalytic application. Although there are few reports on the direct participation of cobalt hydrogen complexes in catalytic reactions, according to the reported literature, the cobalt hydrogen complexes are active intermediates of various catalytic reactions and have great potential for development. In the first part, we studied the reaction of Co (PMe3) 4 with phenylselenol, o-methylphenylselenol and p-methoxyphenylselenol, and successfully obtained four new organic cobalt complexes 1-4 containing selenium. The mechanism of the reaction of Co (PMe3) 4 with phenylselenol ligands was investigated. A new cobalt hydrogen complex 7 was obtained by the reaction of PhSeLi,CoCl (PMe3) 3 and PhSH. By exploring the properties of the newly synthesized organic cobalt complexes containing selenium, it is found that cobalt hydrogen complex 2 has a certain catalytic effect on the hydrosilylation of aldehydes and ketones. Complex 3H4 can be further reacted with CO to obtain cobalt bicarbonyl complexes 5 and 6. In the second part, based on the experimental results in the laboratory, the properties of the ferric hydrogen complexes obtained by the reaction of (o-PPh2) PhSeH with Fe (PMe3) 4 were investigated systematically, and the reaction of the ferric hydrogen complexes with CO was carried out. The carbonyl iron hydrogen complex 8 containing two isomers was isolated. The reaction of ferric hydrogen complex with acetylacetone was studied and the double chelate iron complex 11 was obtained by single crystal diffraction. In addition, the reaction of (o-PPh2) PhSeH with Co (PMe3) _ 4 Cocl (PMe3) _ 3 (PMe3) _ 4 has been studied.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
【参考文献】
相关博士学位论文 前1条
1 周红卫;三甲基膦支持的新型铁、钴、镍氢化合物的合成及性质研究[D];山东大学;2015年
，本文编号：2369634
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